Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
  • C11D17/0017—Multi-phase liquid compositions
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/03—Liquid compositions with two or more distinct layers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/10—Washing or bathing preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/02—Preparations for cleaning the hair
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/825—Mixtures of compounds all of which are non-ionic
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/835—Mixtures of non-ionic with cationic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/88—Ampholytes; Electroneutral compounds
  • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2068—Ethers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2093—Esters; Carbonates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/667—Neutral esters, e.g. sorbitan esters
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols

Definitions

• the present invention relates to aqueous liquid cleansing compositions that are biphasic in nature. More specifically, such compositions are characterized by having (assuming they have been standing a sufficiently long period of time after shaking) both an upper aqueous layer and a separate lower aqueous layer.
• Biphasic liquids defined by the general fact that the liquid is divided into two phases are not new. In some of these liquids one layer is an aqueous layer and the second layer is a water immiscible oily material while in others both layers are aqueous based.
• U.S. Pat. No. 3,718,609 issued to Weimer on Feb. 27, 1973 discloses a liquid detergent composition having an aqueous layer and a layer of liquid water immiscible oily material. When shaken, the liquid forms a temporary oil-in-water emulsion.
• U.S. Pat. No. 3,810,478 issued to Olson Jr. et al on May 14, 1974 discloses a two-phase shampoo composition made by preparing substantially polar and lipophilic portions of a shampoo composition.
• Biphasic compositions comprising an upper and lower aqueous phase are also disclosed in the art.
• U.S. Pat. No. 6,429,177 issued to Williams et. al. on Aug. 6, 2002 discloses biphasic compositions including 5 to 35% surfactant; 1 to 12% thickener; 4 to 20% polyalkylene glycol; and a sufficient amount of non-chelating mineral salt to induce phase separation.
• U.S. Pat. No. 6,180,587 issued to Fuller et. al. on Jan. 30, 2001 disclose multiphase cleansing compositions having at least 1% of a polymer or copolymer selected from the group consisting of polyacrylate, polystyrene sulfonate, polyvinyl-pyrrolidone, maleic anhydride and their mixtures.
• EP 0,116,422 to Harmer published on Apr. 6, 1988 also discloses multi-layered compositions in which two liquids are dispersible and which separate on standing.
• Sodium hexamataphosphate is a preferred biphasic inducing agent required in these compositions.
• polydextrose compositions as well as the compositions described in U.S. Pat. No. 6,429,177 issued to Williams et. al. on Aug. 6, 2002 required a separate thickener to achieve a viscosity suitable for a liquid cleanser especially one targeted to personal cleansing, e.g., shower gel and shampoo.
• biphasic inducing agents that can be used alone or in combination with polydextrose and/or salt. These new BIA fall into two classes.
• One class includes specific polysaccharides that surprisingly have higher molecular weights than the optimal polydextrose oligomers described above.
• the second class includes intermediate ethoxylates of specific fatty esters or fatty ethers.
• the present invention seeks improvements over deficiencies in the known art.
• BIA that induce the formation of aqueous biphasic cleaning liquids that are economical, require no additional thickener and produce an optical transition from clear to opaque when shaken.
• biphasic liquids e.g., liquids that separate into top and bottom aqueous liquids
• BIA Biphasic Inducing Agents
• liquid cleansing compositions include:
• % or wt % refers to percent by weight of an ingredient as compared to the total weight of the composition or component that is being discussed.
• any particular upper concentration can be associated with any particular lower concentration.
• the present invention relates to biphasic liquid cleansing compositions wherein the formation of the biphasic liquid is induced by the addition of sufficient amounts of particular Biphasic Inducing Agents (BIA).
• Biphasic Inducing Agents The general concept behind the invention is that, when sufficient amount(s) of BIA is (are) added, phase separation occurs. For example, this is shown in the Examples wherein, when 3% of a particular polysaccharide, pullulan (MW 200,000) is added, separation occurs.
• Different surfactant systems can be used and the specific type of surfactants is not a limiting factor although the type and level of surfactant can affect the amount of BIA required to induce phase separation in the composition.
• inventive compositions may be used in combination with a transparent package in order to view the liquid.
• the invention is a system including a transparent or translucent package in combination with the liquid.
• the viscosity of the lower layer is generally lower than that of the upper layer.
• the density of lower layer is typically greater than that of upper layer.
• composition after being shaken should preferably have a shower-gel or shampoo like viscosity of 100 to 5000 mPas, more preferably 200 to 4000 mPas at a shear rate 10 s ⁇ 1 at 25° C. as measured with an appropriate viscometer such as a Haake RV20 Rotovisco Rheometer.
• the BIAs of the invention are used with a small amount of salt or salt in combination with a polydextrose or a polyethylene glycol.
• the composition typically includes about 1% to about 10% of a salt and about 2% to about 35% of a polydextrose in addition to the BIA of the invention.
• a salt in addition to the BIA of the invention.
• a polydextrose in addition to the BIA of the invention.
• the surfactant generally will be included at a level from about 5% to about 75% by wt. of the total composition.
• the surfactant may be selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric/zwitterionic surfactants, cationic surfactants and mixtures thereof. Preferably, there will be at least one anionic surfactant.
• anionic surfactants are disclosed in McCutcheon's Detergents and Emulsifiers , North American Edition (1986), published by Allured Publishing Corporation; McCutcheon's Functional materials, North Americas Edition (1992), both of which are incorporated by reference into the subject application.
• anionic surfactants include sarcosinates, sulfates, isethionates, taurates, phosphates, lactylates, glutamates and mixtures thereof.
• isethionates are preferred alkoxyl isethionates such as sodium cocoyl isethionate, sodium lauroyl isethionate and mixtures.
• the alkyl and alkyl ether sulfates typically have the respective formulae ROSO 3 M and RO(C 2 H 4 O) x SO 3 M, wherein R is alkyl or alkenyl of from about 10 to about 30 carbon atoms, x is from about 1 to about 10, and M is a water-soluble cation such as ammonium, sodium, potassium, magnesium and triethanolamine.
• anionic surfactant are the water-soluble salts of the organic, sulfuric acid reaction products of the general formula: R 1 —SO 3 -M wherein R 1 is chosen from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 10 to about 16, carbon atoms; and M is a cation.
• Still other anionic synthetic surfactants include the class designated as succinates and sulfosuccinates, olefin sulfonates having about 12 to about 24 carbon atoms, and ⁇ -alkyloxy alkane sulfonates. Examples of these materials are sodium lauryl sulfate and ammonium lauryl sulfate.
• soaps i.e., alkali metal salts, e.g., sodium or potassium salts or ammonium or triethanolamine salts
• fatty acids typically having from about 8 to about 24 carbon atoms, preferably from about 10 to about 20 carbon atoms.
• the fatty acids used in making the soaps can be obtained from natural sources such as, for instance, plant or animal-derived glycerides (e.g., palm oil, coconut oil, soybean oil, castor oil, tallow, lard, etc.).
• the fatty acids can also be synthetically prepared. Soaps are described in more detail in U.S. Pat. No. 4,557,853.
• phosphates such as monoalkyl, dialkyl, and trialkylphosphate salts.
• alkanoyl sarcosinates corresponding to the formula RCON(CH 3 )CH 2 CH 2 CO 2 M wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, and M is a water-soluble cation such as ammonium, sodium, potassium and alkanolamine (e.g., triethanolamine), a preferred examples of which are sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, ammonium lauroyl sarcosinate, and sodium myristoyl sarcosinate.
• TEA salts of sarcosinates are also useful.
• taurates which are based on taurine, which is also known as 2-aminoethanesulfonic acid. Especially useful are taurates having carbon chains between C 8 and C 16 .
• taurates include N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. No. 2,658,072 which is incorporated herein by reference in its entirety.
• Further non-limiting examples include ammonium, sodium, potassium and alkanolamine (e.g., triethanolamine) salts of lauroyl methyl taurate, myristoyl methyl taurate, and cocoyl methyl taurate.
• lactylates especially those having carbon chains between C 8 and C 16 .
• lactylates include ammonium, sodium, potassium and alkanolamine (e.g., triethanolamine) salts of lauroyl lactylate, cocoyl lactylate, lauroyl lactylate, and caproyl lactylate.
• alkylamino carboxylates such as glutamates and glycinates, especially those having carbon chains between C 8 and C 16 .
• Non-limiting examples include ammonium, sodium, potassium and alkanolamine (e.g., triethanolamine) salts of lauroyl glutamate, lauroyl glycinate, myristoyl glutamate and myristoy glycinate, and cocoyl glutamate and cocoyl glycinate.
• Non-limiting examples of preferred anionic lathering surfactants useful herein include those selected from the group consisting of sodium lauryl sulfate, ammonium lauryl sulfate, ammonium laureth sulfate, sodium laureth sulfate, sodium trideceth sulfate, ammonium cetyl sulfate, sodium cetyl sulfate, ammonium cocoyl isethionate, sodium lauroyl isethionate, sodium lauroyl lactylate, triethanolamine lauroyl lactylate, sodium caproyl lactylate, sodium lauroyl sarcosinate, sodium myristoyl sarcosinate, sodium cocoyl sarcosinate, sodium lauroyl methyl taurate, sodium cocoyl methyl taurate, sodium lauroyl glutamate, sodium myristoyl glutamate, and sodium cocoyl glutamate, and sodium lauroyl glycinate, cocoyl
• ammonium lauryl sulfate ammonium lauryl sulfate, ammonium lauryl ether sulfate, sodium lauryl ether sulfate, sodium lauryl ether sulfosuccinates, sodium methyl 2-sulfolaurate, disodium 2-sulfolaurate, sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium myristoyl sarcosinate, sodium lauroyl lactate, and triethanolamine lauroyl lactylates.
• Non-limiting examples of nonionic lathering surfactants for use in the compositions of the present invention are disclosed in McCutcheon's, Detergents and Emulsifiers , North American Edition (1986), published by allured Published Corporation; and McCutcheon's, Functional materials , North American Edition (1992); both of which are incorporated by reference herein in their entirety.
• Nonionic lathering surfactants useful herein include those selected form the group consisting of alkyl glucosides, alkyl polyglucosides, polyhydroxy fatty acid amides, alkoxylated fatty acid esters, alcohol ethoxylates, lathering sucrose esters, amine oxides, and mixtures thereof.
• Alkyl glucosides and alkylipolyglucosides are useful herein, and can be broadly defined as condensation articles of long chain alcohols, e.g., C8-30 alcohols, with sugars or starches or sugar or starch polymers i.e., glycosides or polyglycosides.
• These compounds can be represented by the formula (S) n —O—R wherein S is a sugar moiety such as glucose, fructose, mannose, and galactose; is an integer of from about 1 to about 1000, and R is a C8-30 alkyl group.
• long chain alcohols from which the alkyl group can be derived include decyl alcohol, cetyl alcohol, stearyl alcohol, lauryl alcohol, myristyl alcohol, oleyl alcohol and the like.
• Preferred examples of these surfactants include those wherein S is a glucose moiety, R is a C8-20 alkyl group, and n is an integer of from about 1 to about 9.
• Commercially available examples of these surfactants include decyl polyglucoside (available as APG 325 CS from Henkel) and lauryl polyglucoside (available as APG 600 CS and 625 CS from Henkel).
• sucrose ester surfactants such as sucrose cocoate and sucrose laurate.
• Nonionic surfactants include polyhydroxy fatty acid amide surfactants, more specific examples of which include glucosamides, corresponding to the structural formula: wherein R 1 is H, C 1 -C 4 alkyl, 2-hydroxyethyl, 2-hydroxy-propyl, preferably C 1 -C 4 alkyl, more preferably methyl or ethyl, most preferably methyl; R 2 is C 5 -C 31 alkyl or alkenyl, preferably C 7 -C 19 alkyl or alkenyl, more preferably C 9 -C 17 alkyl or alkenyl, most preferably C 11 -C 15 alkyl or alkenyl; and Z is a polyhydroxy hydrocarbyl moiety having a linear hydrocarbyl chain with at least 3 hydroxyl directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
• R 1 is H, C 1 -C 4 alkyl, 2-hydroxyethyl, 2-
• Z preferably is a sugar moiety selected from the group consisting of glucose, fructose, maltose, lactose, galactose, mannose, xylose, and mixtures thereof.
• surfactant corresponding to the above structure is coconut alkyl N-methyl glucoside amide (i.e., wherein the R 2 CO-moiety is derived form coconut oil fatty acids).
• Processes for making compositions containing polyhydroxy fatty acid amides are disclosed, for example, in GB Patent Specification 809,060, published Feb. 18, 1959, by Thomas Hedley & Co., Ltd.; U.S. Pat. No. 2,965,576, to E. R. Wilson, issued Dec. 20, 1960; U.S. Pat. No. 2,703,798 to A. M. Schwartz, issued Mar. 8, 1955; and U.S. Pat. No. 1,985,424, to Piggott, issued Dec. 25, 1934; which are incorporated herein by reference in their entirety.
• nonionic surfactants include amine oxides.
• Amine oxides correspond to the general formula R 1 R 2 R 3 N ⁇ O, wherein R 1 contains an alkyl, alkenyl or monohydroxyl alkyl radical of from about 8 to about 18 carbon atoms, and R 2 and R 3 contain from about 1 to about 3 carbon atoms and from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl radicals.
• the arrow in the formula is a conventional representation of a semipolar bond.
• amine oxides suitable for use in this invention include dimethyldodecylamine oxide, oleyl di(2-hydroxyethyl) amine oxide, dimethyloctylamine oxide, dimethyl-decylamine oxide, dimethyl-tetradecylamine oxide, 3,6,9-trioxaheptadecyldiethylamine oxide, di(2-hydroxyethyl)-tetradecylamine oxide, 2-dodecoxyethyldimethylamine oxide, 3-dodecoxy-2-hydroxypropyldi(3-hydroxypropyl)amine oxide, diemethylhexadecyclamine oxide.
• foam boosting amides Another useful class of nonionic surfactant is the foam boosting amides. Although these materials do not lather by themselves they often boost lather when combined with other surfactants such as alkyl ethoxy sulfates.
• suitable amides include coco monoethanol amide, and ethoxyleted coco monoethanol amide, e.g., PEG-5 CMEA.
• Non-limiting examples of preferred nonionic surfactants for use herein are those selected form the group consisting of C 8 -C 14 glucose amides, C 8 -C 14 alkyl polyglucosides, sucrose cocoate, sucrose laurate, lauramine oxide, cocoamine oxide, coco monothanolamide PEG-5 coco monoethanolamide and mixtures thereof.
• amphoteric lathering surfactant is also intended to encompass zwitterionic surfactants, which are well known to formulators skilled in the art as a subset of amphoteric surfactants.
• amphoteric lathering surfactants can be used in the compositions of the present invention. Particularly useful are those which are broadly described as derivatives of aliphatic secondary and tertiary amines. Here preferably the nitrogen is in a cationic state, the aliphatic radicals can be straight or branched chain and one of the radicals contains an ionizable water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
• an ionizable water solubilizing group e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
• Non-limiting examples of amphoteric surfactants useful in the compositions of the present invention are disclosed in McCutcheon's, Detergents and Emulsifiers , North American Edition (1986), published by Allured Publishing Corporation; and McCutcheon's, Functional Materials , North American Edition (1992); both of which are incorporated by reference herein in their entirety.
• Non-limiting examples of amphoteric or zwitterionic surfactants are those selected from the group consisting of betaines, sultaines, hydroxysultaines, alkyliminoacetates, iminodialkanoates, aminoalkanoates, and mixtures thereof.
• betaines include the higher alkyl betaines, such as coco dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, cetyl dimethyl betaine (available as Lonaine 16SP from Lonza Corp.), lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(hydroxypropyl)alpha-carboxyethyl betaine, coco dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl betaine, amidobetaines and amidosulfobetaines (wherein the RCONH(CH 2 ) 3 radical is attached to the nitrogen atom of the betaine), oleyl betaine (available as ammoni
• Example of sultaines and hydroxysultaines include materials such as cocamidopropyl hydroxysultaine (available as Mirataine CBS from Rhodia).
• amphoteric surfactants having the following structure: wherein R 1 is unsubstituted, saturated or unsaturated, straight or branched chain alkyl having from about 9 to about 22 carbon atoms. Preferred R 1 has from about 11 to about 18 carbon atoms; m is an integer from 1 to about 3, more preferably from about 2 to about 3, and more preferably about 3; n is either 0 or 1, preferably 1; R 2 and R 3 are independently selected from the group consisting of alkyl having from 1 to about 3 carbon atoms, unsubstituted or mono-substituted with hydroxy, preferred R 2 and R 3 are CH 3 ; X is selected form the group consisting of CO 2 , SO 3 and SO 4 ; R 4 is selected form the group consisting of saturated or unsaturated, straight or branched chain alkyl, unsubstituted or mono-substituted with hydroxy, having from 1 to about 5 carbon atoms.
• R 4 When X is CO 2 , R 4 preferably has 1 to 3 carbon atoms, more preferably 1 carbon atom. When X is SO 3 or SO 4 , R 4 preferably has from about 2 to about 4 carbon atoms, more preferably 3 carbon atoms.
• amphoteric surfactants of the present invention include the following compounds:
• Cetyl dimethyl betaine (this material also has the CTFA designation cetyl betaine);
• R has from about 9 to about 13 carbon atoms
• R has from about 9 to about 13 carbon atoms.
• Cationic surfactants are another useful class of surfactants that can be employed as auxiliary agents. They are particularly useful as additives to enhance skin feel, and provide skin conditioning benefits.
• One class of cationic surfactants is heterocyclic ammonium salts such as cetyl or stearyl pyridinium chloride, alkyl amidoethyl pyrrylinodium methyl sulfate, lapyrium chloride.
• Tetra alkyl ammonium salts is another useful class of cationic surfactants.
• examples include cetyl or stearyl trimethyl ammonium chloride or bromide; hydrogenated palm or tallow trimethylammonium halides; behenyl trimethyl ammonium halides or methyl sulfates; decyl isononyl dimethyl ammonium halides; ditallow (or distearyl) dimethyl ammonium halides; behenyl dimethy ammonium chloride.
• cationic surfactants that can be employed are the various ethoxylated quaternary amines and ester quats. Examples are PEG-5 stearyl ammonium lactate (e.g., Genamin KSL manufactured by Clarion), PEG-2 coco ammonium chloride, PEG-15 hydrogenated tallow ammonium chloride, PEG 15 stearyl ammonium chloride, dialmitoyl ethyl methyl ammonium chloride, dipalmitoyl hydroxyethyl methyl sulfate, strearyl amidopropyl dimethylamine lactate.
• PEG-5 stearyl ammonium lactate e.g., Genamin KSL manufactured by Clarion
• PEG-2 coco ammonium chloride PEG-15 hydrogenated tallow ammonium chloride
• PEG 15 stearyl ammonium chloride dialmitoyl ethyl methyl ammonium chloride
• Still other useful cationic surfactants are quaternized hydrolysates of silk, wheat, and keratin proteins.
• BIA falling into one of two broad classes of water-soluble materials have been found useful in the practice of the present invention: high-gel-point polysaccharides and intermediate ethoxyltes of fatty esters or fatty ethers.
• the polysaccharides of the invention have a molecular weight of at least about 10,000, preferably greater than 50,000, and most preferably greater than 150,000 Daltons. These polysaccharides are also water soluble, preferably highly water soluble (e.g., dissolve at a level of at least about 10% by weight in water) and most preferably form stable solutions at ambient temperature. The most preferred polysaccharides also form clear isotropic solutions in water at room temperature.
• the polysaccharide should have a high gel point to function optimally as a BIA of the invention. This high gel point is indicative of a low tendency to form gels in water in the sense described below.
• gel is meant a viscoelastic liquid or paste exhibiting an apparent yield stress.
• gel point is meant the concentration in water where the polysaccharide forms a gel at room temperature (about 25° C.).
• high-gel-point polysaccharide is meant a polysaccharides that either will not gel at any concentration or will induce biphasic formation when incorporated into the composition of interest at a lower concentration than is required for the polysaccharide to form a gel in water. This latter condition is generally achieved if the instant polysaccharide BIA have a gel point in water (minimum concentration to produce a viscoelastic liquid exhibiting a yield value) of at least about 2% by weight, more preferably of at least about 5% in water, and most preferably of at least about 10% in water.
• a test to determine the concentration of BIA required to induce phase separation is described in the EVALUATION METHODOLOGY SECTION below.
• suitable polysaccharides tend to be nonionic in character, and tend to have a molecular structure that tends to retard molecular association in water, e.g., branching, kinks or small pendant groups appearing with sufficiently high frequency, i.e., short repeat lengths.
• Pullulan is a class of glucans elaborated extracellularly by the fungus Aureobasidium (also known as Pullularia). Pullulan dissolves readily in water to form stable viscous solutions that do not gel.
• Pullan The structure of Pullan is reported to be predominantly based on maltotriose units joined by ⁇ -D-(1-6) linkages.
• the molecular weight of pullulan an can vary between 1,000 to 3,000,000 Daltons. However, for the purposes of the present application, the molecular weight should be greater than about 10,000, preferably greater than 50,000 and most preferably between 100,000 and 300,00 Daltons.
• Pullulan is available from Hayashibara and sold under the trade name Pullulan PI 20. A particular pullulan from Hayashibara having an average molecular weight of 200,000 was suitable.
• a second useful polysaccharide is one derived from high amylopectin starch.
• Amylopectin is one of the primary polysaccharide polymer components of starch, the other polysaccharide polymer component being amylose.
• Amylopectin molecules have a branch-on-branch structure and are composed of chains of ⁇ -D-(1-4) linked glucopyranose of various lengths joined via unequally spaced ⁇ -D-(1-6) linkages.
• the molecular weight of amylopectin as it occurs in starch is purported to be in the range from about 5 ⁇ 10 7 to about 4 ⁇ 10 8 Daltons.
• Amylopectin in contrast with amylose, forms clear stable solutions (e.g., little retrogradation) when heated to a sufficiently high temperature and either does not form gels or only forms weak gels).
• High amylopectin starches are available commercially as waxy variants (mutants) of corn, wheat and rice starch among others.
• Amylopectin-rich starches can also be modified to reduce molecular weight (e.g., heating solutions under high shear or partial hydrolysis with acid), or to make them more cold water soluble (e.g., gelatinized starch).
• modified waxy starch include depolymerized or “thinned” waxy corn and pregelatinized waxy corn. Both modified waxy starches can be obtained for example, from National Starch and Chemicals.
• polysaccharides is depolymerized or thinned starch. These materials differ from polydextroses in the degree of depolymerization—see below).
• the thinned starches generally have an average degree of polymerization of greater than 60, which corresponds to a molecular weight greater than about 10,000 Daltons.
• depolymerized starches examples include: acid-modified starch which are generally formed by treating native or modified starch granules with dilute mineral acid at a temperature below that required for gelatinization; enzyme-converted starch which are starches treated with alph-amylase (or isoamylase to reduce branching) to achieve a lower viscosity, clearer aqueous mixture; oxidized starch treated with for example, ammonium persulfate; and thermomechanical degraded starches—slurry heated to high temperature under high shear.
• Still another useful class of polysaccharide is exudate gums.
• An example of a useful exudate gum is gum arabic, which is a gum exuded from the bark of the Acacia tree. Gum arabic, is readily soluble in cold water, does not form gels, and forms clear solutions which have a relatively low viscosity.
• One especially suitable high-gel-point polysaccharide is pullulan.
• a second class of useful BIA is the intermediate ethoxylates of fatty esters or fatty ethers.
• intermediate ethoxylates ethoxylates that are longer than typical alcohol ethoxylate nonionic surfactants (greater than about 12, preferably greater than about 15), but lower than hydrophobically modified polyoxyethylene copolymers that are used as thickeners (lower than about 100, preferably lower than about 70).
• the degree of ethoxylation (defined as moles ethylene oxide per molecule) of the intermediate fatty ethoxylate is in the range from about 10 to about 80, preferably about 15 to about 45 and most preferably from about 15 to 35 moles ethylene oxide per molecule.
• fatty ester or “fatty ether” is meant esters or ethers that incorporate “fatty chains” by which is generally meant one or more straight or branched alkyl or alkenyl chains having from about 8 to about 22 carbon atoms.
• Suitable fatty ester intermediate ethoxylates include the C 12 -C 22 saturated or unsaturated fatty acid mono and diglyceride ethoxylates with an average of 20 to 80 units or moles ethylene oxide per molecule.
• Examples include ethoxylated castor oil, ethoxylated soya oil glycerides, and ethoxylated olive oil glycerides, and ethoxylated palm kernal glycerides.
• Examples include PEG-30 castor oil, PEG-40 hydrogenated castor oil, PEG 36-soya glycerides, PEG-75 Soya ethoxylate, PEG-40 olive oil glycerides, and PEG-47 palm kernal glycerides.
• Another fatty ester intermediate ethoxylate includes the C 12 -C 22 saturated or unsaturated fatty acid sorbitan esters having about 20 to about 80 moles of ethylene oxide per molecule.
• Examples include PEG-40 sorbitan laurate, PEG-75 sorbitan monolaurate, PEG-40 sorbitan trioleate, and PEG-50 sorbitan laurate.
• Another fatty ester intermediate ethoxylate is a C 12 -C 22 fatty acid ethoxylated with an average of about 20 to about 50 ethylene oxide units.
• Fatty ether intermediate ethoxylates include C 12 -C 22 saturated or unsaturated (preferably saturated) fatty alcohols ethoxylated with an average of about 12 to about 80 ethylene oxide units. Examples include steareth-25, steareth-50, laureth-40, and beheneth-30.
• Castor oil ethoxylate having 20 to 50 moles ethylene oxide is a particularly suitable fatty ester intermediate ethoxylate.
• the level of BIA required depends on the cleanser composition and upon the ratio of the separate aqueous phases that is desired. Thus, for example, if the composition contains salt, or a polydextrose of molecular weight less than 3600 Daltons, as little as 0.5% of a non-gelling polysaccharide of the invention may be required by weight of composition while 2-10%, preferably 2-5%, may be required in the absence of the salt and polydextrose. Furthermore, when the non-gelling polysaccharide and fatty intermediate ethoxylate are combined, the levels of each separate BIA required will vary according to the combination.
• the level of high-gel-point polysaccharide required will generally be about 0.25 to about 20%, preferably 0.25 to about 10% and most preferably about 0.5% to about 5% based on the total weight of the composition, i.e., all phases taken together.
• the level of fatty intermediate ethoxylate required will generally be about 0.5 to about 15%, preferably 0.5 to about 10% and most preferably about 0.1% to about 5% based on the total weight of the composition, i.e., all phases taken together.
• surfactant used and amount of BIA.
• 5% to 10% by wt. surfactant may require about 5-10% high-gel-point polysaccharide while 10%-20% surfactant may need only about 1-5% of the same low-gelling polysaccharide.
• Polydextrose is a relatively low molecular weight, generally branched polymer primarily composed of D-glucose:
• n (defining number of linking glucose units) is from about 4 to about 22.
• polydextrose includes maltodextrin, which is formed by the extensive depolymerization of starch through, for example, dry-roasting, and synthetic poydextrose which is formed by heating dextrose (glucose) with an acid catalyst.
• Polydextrose having a MW in the range of from 600 to about 3600, more preferably 700 to 3000, more preferably 700 to 1800, and even more preferably 900 to 1500 is known to induce the formation of biphasic liquids on its own.
• These polymers are also highly suitable for use in combination with the BIA of the present invention and can be used to advantage to improve the overall composition and its economics.
• Electrolytes preferably, non-chelating electrolyte (chelating electrolytes have generally poorer biodegradability), are also useful in combination with the instant BIA.
• the electrolyte should be a salt of a sulphate, bisulfate, carbonate, bicarbonate, phosphate, chloride, etc.
• examples include sodium sulphate, potassium sulphate, ammonium sulphate, sodium chloride, and magnesium chloride.
• Magnesium sulphate and sodium chloride are particularly preferred.
• the composition may contain polyalkylene glycol.
• the polyalkylene glycol should be an alcohol, glycol or polyether of minimal molecular weight which is not irritating to the skin.
• Examples of such include alcohols, particularly polyalkylene oxides having MW 200-6000, preferably 200 to 3000.
• the polyalkylene glycol can be comprised of ethylene oxide, propylene oxide, butylene oxide or their mixtures either as polymers or copolymers. Specific examples include polyethylene glycols such as PEG 400. As noted, use of such alcohols is not required.
• composition may further comprise thickeners.
• thickener/viscosity modifier serves to thicken the upper and/or lower layer.
• Thickeners which may be used include hydrophobically modified polyethers.
• examples of this class of thickeners which may be used include but are not limited to sugar esters such as PEG (160) sorbitan triisostearate (Rheodol TWS-399C ex Kao Chemicals) or PEG-120 Pentaerythrityl Tetrastearate ex Croda.
• Other examples include Glucam DOE 120 (PEG 120 Methyl Glucose Dioleate); Rewoderm® (PEG modified glyceryl cocoate, palmate or tallowate) from Rewo Chemicals; Antil® 141 (from Goldschmidt); and Carbopol® polymers from Noveon.
• hydrophobically modified cellulose ethers including but not limited to hydroxyethyl cellulose, hydroxypropylcellulose and cellulose ethers with long pendant chains such as nonoxynyl hydroxyethylcellulose (Amerchol Polymer HM 1500).
• hydrophobically modified acrylate copolymers such as Antil 208® (ex Goldschmidt) (acrylate/steareth-50 acrylate copolymer).
• Suitable polymers is the hydrophobically modified polyurethanes such as Acrysol series (e.g., Acrysol RM-2020) from Rhom and Haas.
• Acrysol series e.g., Acrysol RM-2020
• Another class of suitable thickeners is gums such as xanthan gums, guar gums and chemically modified guar gums.
• compositions of the invention may contain hydrotropes including but not limited to short chain monohydric or dihydric alcohols, xylene sulphonate and hexylene glycol whose purpose is to avoid the formation of liquid crystal phases resulting from the separation of the surfactant material into the upper phase hence increasing its apparent concentration.
• hydrotropes including but not limited to short chain monohydric or dihydric alcohols, xylene sulphonate and hexylene glycol whose purpose is to avoid the formation of liquid crystal phases resulting from the separation of the surfactant material into the upper phase hence increasing its apparent concentration.
• compositions may comprise benefit agents.
• Benefit agent may be any material that has potential to provide an effect on, for example, the skin and/or the hair.
• the benefit agent may be water insoluble material that can protect, moisturize or condition skin or hair upon deposition from compositions of invention.
• These may include silicon oils and gums, fats and oils, waxes, hydrocarbons (e.g., petrolatum), higher fatty acids and esters, vitamins, sunscreens. They may include any of the agents, for example, mentioned at column 8, line 31 to column 9, line 13 of U.S. Pat. No. 5,759,969, hereby incorporated by reference into the subject application.
• the benefit agent may also be a water soluble material such as glycerin, polyols (e.g., saccharides), enzyme and ⁇ - or ⁇ -hydroxy acid either alone or entrapped in an oily benefit agent.
• glycerin e.g., glycerin, polyols (e.g., saccharides), enzyme and ⁇ - or ⁇ -hydroxy acid either alone or entrapped in an oily benefit agent.
• the benefit agent may be found in either the upper or the lower layer depending on its solubility and partition coefficient, for example, oil may partition into the upper layer while more water soluble agents (e.g., ⁇ -hydroxyacids) may go into the lower.
• oil may partition into the upper layer while more water soluble agents (e.g., ⁇ -hydroxyacids) may go into the lower.
• compositions may comprise perfumes, sequestering agents such as EDTA, EHDP in amounts 0.01 to 1%, preferably 0.01 to 0.05%; coloring agents, opacifiers and pearlizers such as zinc stearate, magnesium stearate, TiO 2 , mica, EGMS (ethylene glycol monostrearate) or styrene/acrylate copolymers.
• perfumes sequestering agents such as EDTA, EHDP in amounts 0.01 to 1%, preferably 0.01 to 0.05%
• coloring agents, opacifiers and pearlizers such as zinc stearate, magnesium stearate, TiO 2 , mica, EGMS (ethylene glycol monostrearate) or styrene/acrylate copolymers.
• compositions may further comprise antimicrobials such as 2-hydroxy 4,2′4′ trichlorodiphenylether (DP300), 3,4,4′-trichlorocarbanilide, essential oils and preservatives such as dimethyl hydantoin (Glydant XL 1000), anti-dandruff agents, parabens, sorbic acid etc.
• antimicrobials such as 2-hydroxy 4,2′4′ trichlorodiphenylether (DP300), 3,4,4′-trichlorocarbanilide, essential oils and preservatives such as dimethyl hydantoin (Glydant XL 1000), anti-dandruff agents, parabens, sorbic acid etc.
• compositions may also comprise coconut acyl mono or diethanol amides as suds boosters, and strongly ionizing salts such as sodium chloride and sodium sulfate may also be used to advantage.
• Antioxidants such as, for example, butylated hydroxytoluene (BHT) may be used advantageously in amounts of about 0.01% or higher if appropriate.
• BHT butylated hydroxytoluene
• Cationic conditioners which may be used including Quatrisoft LM-200 Polyquaternium-24, Merquat Plus 3330-Polyquaternium 39; and Jaguar® type conditioners.
• Composition may also include clays such as Bentonite® claims as well as particulates such as abrasives, glitter, and shimmer agents (e.g., micas).
• clays such as Bentonite® claims
• particulates such as abrasives, glitter, and shimmer agents (e.g., micas).
• the balance of the composition is generally water.
• compositions of the invention when unmixed, have a viscosity of the lower layer which is generally lower than the viscosity of the upper layer and a density of the lower layer which is greater than the density of the upper layer.
• compositions of the invention in a separated state, are also stable in that no recrystallization (e.g., in the lower layer) occurs even when left sitting for more than 6 months at temperature of 0° C.
• compositions of the invention have an experiential element in that they are intended to be agitated by the consumer to mix and form a single visible phase before separating again after a time, anywhere from about a few seconds to not more than about 24 hours.
• the packages in which the compositions are contained is preferably translucent or transparent.
• the materials e.g., plastics
• the package should be sufficiently transparent to permit the separation of the two or more layers to be visible to the naked eye.
• Viscosity was measured with a Haake model RV 20 Rotovisco rheometer which includes a stand and sample temperature control unit, cups and bobs for loading the sample, a water bath which is maintained at 25° C. and a computer and plotter to manipulate and record the data.
• a NV cup/bob assembly is employed for viscosity measurements of low viscous products, e.g. diluted solutions, fruit juices, etc.
• An SV1 cup/bob assembly is employed for viscosity measurements of intermediate viscosity liquids, e.g., typical shower gel or shampoo products;
• the viscosity was measured as follows. The rotor (bob) was secured to the top segment of the viscometer and the RV 20 viscometer was adjusted using the zero button. A test sample was poured into the cup until almost three fourths filled (approx. 20 g). If the test sample is a biphasic liquid it was vigorously stirred but with minimum air bubble entrapment. In a control experiment the liquid was first allowed to sit undisturbed for the same amount of time as would be required to complete a viscosity measurement. If no detectable separation was observed during this period, a fresh biphasic sample was vigorously stirred as above and loaded into the viscometer cup.
• the cup was carefully slid through the temperature controller and screwed to the main segment of the rheometer so that the rotor was immersed in the product and sample was slightly above the rim of the rotor. After 5 to 10 minutes equilibration, a programmed stress-strain sweep was initiated. Generally four shear-rate-segments consisting of 10 steps each were selected. The shear rates were 1, 10, 100, 400 sec ⁇ 1 .
• the viscosity was computed from the measured rheogram and expressed as mPas (cps) at each of the four shear rates.
• a surfactant solution is prepared at about 5 wt. % to about 35.0 wt. % that contained any additional desired ingredients.
• the composition is allowed to equilibrate undisturbed overnight to confirm that no phase separation occurrs, i.e., a stable single-phase composition and not a biphasic liquid is formed.
• the composition is then divided into two parts. To one part is added an appropriate amount of a candidate BIA, e.g., pullulan, to produce a desired concentration, e.g., 3 wt % (generally but not always the candidate BIA is added via a solution). This resulting composition is termed the “Test Composition”.
• the other part serves as a “Reference Composition” once the same weight of water is added as the combined weight of water plus candidate BIA that is added to make the “Test Composition”.
• Test and Reference compositions each in sealed containers are then stirred for 1 hour at 60° C. until homogeneous and then are allowed to equilibrate overnight. The samples are then evaluated for phase separation.
• a Test Composition must exhibit at least two aqueous phases while its corresponding Reference Composition exhibits only one aqueous phase.
• the above experiment can then be repeated any number of times at a lower or higher BIA concentration in the test composition.
• the lowest BIA concentration that just induces visible phase separation is termed the “Minimum Biphasic Induction Concentration” (MBIC).
• MBIC Minimum Biphasic Induction Concentration
• a series of solution pairs are prepared and tested at the same time to determine the MBIC.
• the MBIC of the polysaccharide Biphasic Inducing Agent of the invention should be lower than its gel point in water.
• compositions are evaluated for viscosity using the method described above. The compositions are also observed for any discoloration and re-crystallisation of saccharides at room temperature. Finally, relative opacity of a biphasic composition contained in a standard clear glass container is determined by eye just after it is shaken.
• the pullulan composition does not require an additional thickener to achieve a similar viscosity of the shaken biphasic liquid.
• Ex 1 has numerically the highest viscosity of the biphasics shown even though it contains the lowest total amount of BIA and no additional thickener.
• Examples 2-4 illustrate the ability of a fatty ester of intermediate ethoxylation to induce the formation of biphasic liquid cleanser when sustituted for water in a single aqueous phase Reference Composition, C4.
• the compositions were prepared by the methods described above. The compositions and results are set forth in Table 2 below.
• Example 5 and 6 illustrate the use of Pullulan in combination with other biphasic inducing agents.
• the compositions Ex 5, Ex 6, C5 and C6 were prepared by the methods described above. The compositions and results are set forth in Table 3.
• Examples 7-8 illustrates the ability of other high gel point polysaccharides to induce the formation of biphasic liquid cleanser when incorporated into a single aqueous phase reference composition, C7.
• the compositions were prepared by the methods described above. The compositions and results are set forth in Table 4 below.
• N-Oil® is a tapioca dextrin
• N-Lite® is a dextrin derived from waxy maize
• HI MAIZE 260 is an acid thinned corn starch, all available from National Starch and Chemicals. All these high-gel-point polysaccharides have an average molecular weight greater than 10,000 Daltons.
• Examples 9-10 illustrate the ability of other intermediate ethoxylate fatty esters to induce the formation of biphasic liquid cleanser when incorporated into a single aqueous phase reference composition, C8.
• the compositions were prepared by the methods described above. The compositions and results are set forth in Table 5 below.
• Example 11-15 in Table 6 further illustrate compositions of the invention TABLE 6 Compositions and results for Examples 11-15 INGREDIENTS Ex 11 Ex 12 Ex 13 Ex 14 Ex 15 SURFACTANT Wt % Sodium Laureth Sulfate 10 10 10 10 Cocoamidopropylbetaine 3 3 3 3 Ammonium Laureth sulfate 4.6 (1/2 EO) Ammonium Lauryl sulfate 6.1 Cocomonoethanolamide 1.0 PEG-5 0.5 cocomonoethanolamide Alpha-step BSS-45 a 2 MgSO 4 3 5 3 3 4 Maltrin M180 10 10 15 BIPHASIC INDUCING AGENT OF INSTANT INVENTION Pullulan 1 3 Gum Arabic 10 5 HI MAIZE 260 15 5 Waxy maize (partially 2 3 oxidized) PEG 50 Sorbitan laurate 2 1 Laureth 50 3 1 PEG 30 Castor oil 2 ADJUNCT INGREDIENTS Perfume, colorant, 1.5 1.5 1.5 1.5 1.5 preservatives WATER

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• 2004
  • 2004-12-28 US US11/023,839 patent/US20060140897A1/en not_active Abandoned
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